EP1273621B1 - Flame-retardant polyolefin resin composition - Google Patents

Flame-retardant polyolefin resin composition Download PDF

Info

Publication number
EP1273621B1
EP1273621B1 EP02710515A EP02710515A EP1273621B1 EP 1273621 B1 EP1273621 B1 EP 1273621B1 EP 02710515 A EP02710515 A EP 02710515A EP 02710515 A EP02710515 A EP 02710515A EP 1273621 B1 EP1273621 B1 EP 1273621B1
Authority
EP
European Patent Office
Prior art keywords
polyolefin resin
parts
resin composition
flame
flame retarded
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02710515A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1273621A1 (en
EP1273621A4 (en
Inventor
Makoto Teramoto
Hideaki Onishi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DKS Co Ltd
Original Assignee
Dai Ichi Kogyo Seiyaku Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dai Ichi Kogyo Seiyaku Co Ltd filed Critical Dai Ichi Kogyo Seiyaku Co Ltd
Publication of EP1273621A1 publication Critical patent/EP1273621A1/en
Publication of EP1273621A4 publication Critical patent/EP1273621A4/en
Application granted granted Critical
Publication of EP1273621B1 publication Critical patent/EP1273621B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines

Definitions

  • This invention relates to a flame retarded polyolefin resin composition. Particularly, it relates to a flame retarded polyolefin resin composition which is less susceptible to bleeding and blooming by flame retardants incorporated therein.
  • Polyolefin resins such as polyethylene or polypropylene have many of desirable properties for fabricating various articles and parts such as containers, mechanical parts, electric and eletronic parts, automobile parts and the like. These properties include, among others, high resistance to water and chemicals, electrical insulation property, high mechanical strength and high processability for fabrication. Polyolefins consist solely of carbon and hydrogen atoms and, therefore, inflammable. For use in a field of application that requires flame retardancy, a flame retardant is incorporated into the polyolefin resin.
  • JP-A-04285647 discloses a flame retarded polypropylene composition including 2,2-bis[4-(2,3-dibromopropoxy)-3,5-dibromophenyl] propane and a benzylidene derivative of sorbitol or xylitol.
  • JP-A-10182889 discloses a flame retarded polyolefin composition including a halogen-containing flame retardant and a polymer containing aromatic hydrocarbon monomer such as styrene.
  • the present invention provides a flame retarded resin composition
  • a flame retarded resin composition comprising (A) a polyolefin resin; (B) 1 to 40 parts by weight per 100 parts of (A) of a brominated bisphenol derivative of the formula: wherein R is hydrogen or methyl, and A is -C(CH 3 ) 2 -, -SO 2 -, -S- or -CH 2 -; and (C) 1 to 30 parts by weight per 100 parts of (A) of 2,4,6-tris(mono-, di- or tribromophenoxy) triazine.
  • components (B) and (C) themselves are a bromine-containing flame retardant. When either of them is incorporated alone into the polyolefin resin to achieve a desired level of flame retardancy, it tends to cause bleeding or blooming. Surprisingly, it was found that combined use of components (B) and (C) in amounts sufficient to achieve a desired level of flame retardancy does not develop bleeding and blooming in articles fabricated from polyolefin resin containing the same.
  • polyolefin resins refers to homo- or copolymers of an aliphatic unsaturated hydrocarbon monomer such as ethylene, propylene, butene, pentene, isoprene or butadiene. Typical examples thereof include polypropylene, polyethylene and ethylene-propylene copolymer. Polypropylene and high density polyethylene are of particular interest.
  • Mixture of the above compounds may also be employed. Some of them are commercially available and others may be synthesized by etherifying a corresponding tetrabromobisphenol with allyl chloride or methallyl chloride followed by addition of bromine to the allyl or methallyl double bond of the resulting allyl ether.
  • 2,4,6-Triphenoxytriazines having up to three bromo substituents on each phenoxy group may be employed. They are synthesized by reacting cyanuric chloride with mono-, di- or tribromophenol. 2,4,6-Tris(2,4,6-tribromophenoxy)triazine, 2,4,6-Tris(2,6-dibromophenoxy)triazine or a mixture thereof is preferable.
  • Proportions of components (B) and (C) per 100 parts by weight of polyolefin resin (A) are 1 to 40 parts by weight and 1 to 30 parts by weight, respectively.
  • the flame retardancy levels depend on the combined proportions of components (B) and (C) in the composition while it is necessary for them to be present in the composition in a certain range of ratio in order to prevent bleeding and blooming.
  • the proportions of components (B) and (C), however, should not be excessive provided that a desired level of flame retardancy is achieved because they have adverse effect on the mechanical strength of articles fabricated from the composition. Taking these factors into consideration, preferable proportions of components (B) and (C) per 100 parts of polyolefin resin (A) are 3 to 25 parts by weight and 5 to 20 parts by weight, respectively.
  • the flame retarded polyolefin resin composition of the present invention may optionally comprise additives other than components (B) and (C).
  • additives other than components (B) and (C) for example, antimony trioxide is known to enhance the flame retardancy of halogen-containing flame retardants.
  • the composition of the present invention may also comprise antimony trioxide or other auxiliary flame retardants. When used, the amount of antimony trioxide is preferably 0.1 to 1.0 times by weight of the combined weights of component (B) and (C).
  • Addition of a brominated epoxy resin is effective to eliminate or decrease percent bleeding when compared at the same level of addition of components (B) and (C).
  • the brominated epoxy resin is also effective as a heat stabilizer during fabrication step of the composition.
  • the amount of brominated epoxy resin should be less than 20 parts by weight, preferably 1 to 15 parts by weight per 100 parts by weight of polyolefin resin (A).
  • Copolymers of olefin and a polar group-containing vinyl monomer such as ethylene-(meth)acrylic acid copolymer, ethylene-alkyl(meth)acrylate copolymer or ethylene-vinyl acetate copolymer, and copolymers, block copolymers in particular, of olefin and an aromatic hydrocarbon monomer such as ethylene-styrene copolymer, ethylene-propylene-styrene copolymer, isoprene-styrene copolymer, ethylene-isoprene-styrene copolymer or hydrogenated butadiene-styrene copolymer are also effective to decrease percent bleeding when compared at the same level of addition of components (B) and (C).
  • a polar group-containing vinyl monomer such as ethylene-(meth)acrylic acid copolymer, ethylene-alkyl(meth)acrylate copolymer or ethylene-vin
  • copolymers may affect the flame retardancy because they are free of bromine content. They also affect the strength properties of fabricated articles. Accordingly, the amount of these copolymers, when used, should be less than 50 parts by weight, preferably 3 to 30 parts by weight per 100 parts by weight of polyolefin resin (A).
  • halogenated polyolefins such as chlorinated polyethylene or chlorinated polypropylenes are also effective to decrease percent bleeding when used less than 50 parts by weight, preferably 3 to 30 parts by weight per 100 parts by weight of polyolefin resin (A).
  • the flame retarded polyolefin resin composition of the invention may comprise a variety of conventional additives for polyolefin resin such as antioxidants, heat stabilizers, UV absorbers, UV stabilizers, pigments, fillers, lubricants, anti-dripping agents, nucleating agents or antistatic agents. Small proportions of known flame retardants other than components (B) and (C) may also be added.
  • the flame retarded polyolefin resin composition of the present invention may be produced by the conventional process such as by mixing the resin and various additives and milling the mixture under heat to obtain a homogenous compound using a machine such as twin screw extruders, Bunbary mixer or hot rolls. Some additives may be premixed and then added to the resin together with the remaining additives. The resulting compound may be shaped to a desired article by injection molding, hot pressing and other shaping methods.
  • Halogenated polyolefin Chlorinated polyethylene (chlorine content 30 wt. %) available from Daiso Co., Ltd. under the name of DAISOLAC U303.
  • the vertical flaming test according to UL-94 standard was followed using a specimen having 127mm length, 12.7 mm width and 1.6 mm thickness.
  • a specimen of 70 x 50 x 3.2 mm size was aged at 80°C for one week. The degree of bleeding was visually observed after aging and judged according to the following criteria. N: Not observed; S: Slightly observes; W: Whitened

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP02710515A 2001-03-19 2002-02-05 Flame-retardant polyolefin resin composition Expired - Lifetime EP1273621B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2001077812 2001-03-19
JP2001077812 2001-03-19
PCT/JP2002/000938 WO2002074852A1 (fr) 2001-03-19 2002-02-05 Composition de résine polyoléfinique ignifuge

Publications (3)

Publication Number Publication Date
EP1273621A1 EP1273621A1 (en) 2003-01-08
EP1273621A4 EP1273621A4 (en) 2005-01-26
EP1273621B1 true EP1273621B1 (en) 2006-09-20

Family

ID=18934507

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02710515A Expired - Lifetime EP1273621B1 (en) 2001-03-19 2002-02-05 Flame-retardant polyolefin resin composition

Country Status (10)

Country Link
US (1) US6924331B2 (ja)
EP (1) EP1273621B1 (ja)
JP (1) JP3968471B2 (ja)
KR (1) KR100640708B1 (ja)
CN (1) CN1194035C (ja)
AT (1) ATE340217T1 (ja)
DE (1) DE60214798T2 (ja)
MY (1) MY127801A (ja)
TW (1) TW588082B (ja)
WO (1) WO2002074852A1 (ja)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050215695A1 (en) * 2004-03-29 2005-09-29 Goossens Danielle F Stabilized flame retardant additives and their use
JP4914000B2 (ja) * 2004-11-12 2012-04-11 株式会社ジェイエスピー ポリスチレン系樹脂押出発泡板
JP2008179741A (ja) * 2007-01-26 2008-08-07 Dai Ichi Kogyo Seiyaku Co Ltd 難燃性オレフィン系樹脂組成物
CN101456994B (zh) * 2007-12-14 2011-05-11 金发科技股份有限公司 一种阻燃聚丙烯树脂共混物及其制备方法
WO2011122428A1 (ja) * 2010-03-31 2011-10-06 リンテック株式会社 ダイシングシート用基材フィルムおよびダイシングシート
WO2013062035A1 (ja) * 2011-10-26 2013-05-02 日本ポリプロ株式会社 熱可塑性樹脂組成物およびそれからなる便器部品

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2506278B2 (ja) 1991-04-25 1996-06-12 第一工業製薬株式会社 難燃性熱可塑性樹脂組成物
US5216059A (en) 1992-04-13 1993-06-01 Great Lakes Chemical Corp. Flame retardant additive composition useful with polyolefins
JPH05320439A (ja) 1992-05-19 1993-12-03 Teijin Chem Ltd 難燃性ポリプロピレン組成物
JPH05339470A (ja) 1992-06-09 1993-12-21 Dainippon Ink & Chem Inc 難燃剤及び難燃性オレフィン系樹脂組成物
JPH06299007A (ja) 1993-04-19 1994-10-25 Marubishi Yuka Kogyo Kk 難燃性ポリオレフィン樹脂組成物
JPH06322280A (ja) 1993-05-13 1994-11-22 Dai Ichi Kogyo Seiyaku Co Ltd 難燃性熱可塑性樹脂組成物
DE4435402A1 (de) 1994-10-04 1996-04-11 Thyssen Draht Ag Verfahren zur Oberflächenbeschichtung von Profildrähten
JPH10316803A (ja) 1997-05-16 1998-12-02 Teijin Chem Ltd 難燃性樹脂組成物

Also Published As

Publication number Publication date
WO2002074852A1 (fr) 2002-09-26
KR20030001499A (ko) 2003-01-06
JPWO2002074852A1 (ja) 2004-07-08
ATE340217T1 (de) 2006-10-15
CN1458955A (zh) 2003-11-26
CN1194035C (zh) 2005-03-23
US6924331B2 (en) 2005-08-02
DE60214798T2 (de) 2007-09-20
US20030139507A1 (en) 2003-07-24
JP3968471B2 (ja) 2007-08-29
TW588082B (en) 2004-05-21
EP1273621A1 (en) 2003-01-08
MY127801A (en) 2006-12-29
EP1273621A4 (en) 2005-01-26
DE60214798D1 (de) 2006-11-02
KR100640708B1 (ko) 2006-10-31

Similar Documents

Publication Publication Date Title
US6737456B2 (en) Fire-retardant polyolefin compositions
JP2002322322A (ja) 難燃性ポリオレフィン組成物
EP1273621B1 (en) Flame-retardant polyolefin resin composition
JP2008179741A (ja) 難燃性オレフィン系樹脂組成物
EP1273622B1 (en) Flame-retardant polyolefin resin composition
US8604106B2 (en) Polypropylene based formulations
US6992129B2 (en) Non-halogenated flame retardant material
JP3156349B2 (ja) ポリオレフィン系樹脂組成物
JP2845692B2 (ja) 難燃性樹脂組成物
WO2001098408A1 (en) Flame-retardant polypropylene resin composition
JP2004099780A (ja) 難燃性ポリオレフィン系樹脂組成物
KR100801823B1 (ko) 난연성 폴리프로필렌 수지조성물
JPH11158329A (ja) 難燃性樹脂組成物
JPH05339447A (ja) プロピレン系樹脂組成物
JP3015574B2 (ja) 難燃性樹脂組成物
JP2857109B2 (ja) 難燃性樹脂便器
WO2023112812A1 (ja) 難燃剤組成物、難燃性樹脂組成物および成形品
WO2001007511A2 (en) Non-blooming, stabilized flame retardant compositions and method of flame retarding polyolefins
JP3503354B2 (ja) 難燃性ポリプロピレン樹脂成形材料、及びポリプロピレン樹脂成形品
JPH08109287A (ja) 難燃性樹脂組成物
WO2001007510A2 (en) Non-blooming, stabilized flame retardant compositions and method of flame retarding polyolefins
JPH08325412A (ja) 難燃化オレフィン系樹脂組成物
IL141726A (en) Polyolefin flame retardant compositions

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20021022

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

A4 Supplementary search report drawn up and despatched

Effective date: 20041209

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060920

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060920

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060920

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060920

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060920

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060920

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20060920

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60214798

Country of ref document: DE

Date of ref document: 20061102

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20061220

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20061220

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20061231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070228

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070312

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20070621

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070205

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20061221

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070205

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060920

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060920

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20100223

Year of fee payment: 9

Ref country code: IT

Payment date: 20100213

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20100211

Year of fee payment: 9

Ref country code: GB

Payment date: 20100202

Year of fee payment: 9

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20110205

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20111102

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110205

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60214798

Country of ref document: DE

Effective date: 20110901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110205

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110901